CN111760584A - Preparation method of novel picoline catalyst - Google Patents
Preparation method of novel picoline catalyst Download PDFInfo
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- CN111760584A CN111760584A CN202010662908.4A CN202010662908A CN111760584A CN 111760584 A CN111760584 A CN 111760584A CN 202010662908 A CN202010662908 A CN 202010662908A CN 111760584 A CN111760584 A CN 111760584A
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- silicate
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- picoline
- novel
- aluminum silicate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 244000282866 Euchlaena mexicana Species 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 4
- -1 compound silicate Chemical class 0.000 claims abstract description 3
- 238000000643 oven drying Methods 0.000 claims abstract description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 30
- 239000004110 Zinc silicate Substances 0.000 claims description 8
- 235000019352 zinc silicate Nutrition 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 6
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000391 magnesium silicate Substances 0.000 claims description 5
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 5
- 235000019792 magnesium silicate Nutrition 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 claims 2
- 238000009472 formulation Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 150000004760 silicates Chemical class 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000002808 molecular sieve Substances 0.000 abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 6
- 239000000575 pesticide Substances 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 1
- WOXFMYVTSLAQMO-UHFFFAOYSA-N 2-Pyridinemethanamine Chemical class NCC1=CC=CC=N1 WOXFMYVTSLAQMO-UHFFFAOYSA-N 0.000 description 1
- 239000005906 Imidacloprid Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229940056881 imidacloprid Drugs 0.000 description 1
- YWTYJOPNNQFBPC-UHFFFAOYSA-N imidacloprid Chemical compound [O-][N+](=O)\N=C1/NCCN1CC1=CC=C(Cl)N=C1 YWTYJOPNNQFBPC-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
- C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a novel picoline catalyst, which comprises the following steps: step 1: stirring water, concentrated hydrochloric acid and P123 at 25-50 deg.C for 0.5-4 hr; step 2: slowly dripping TEOS into the obtained solution for 10-24h, adding silicate containing metal ions and a compound silicate solution, and stirring the solution for 24-48h to obtain a milky suspension; and step 3: transferring the suspension into a self-pressure kettle, crystallizing at 60-120 deg.C for 24-48h, vacuum filtering, and oven drying at 40-70 deg.C; and 4, step 4: obtaining the SBA-15 molecular sieve catalyst loaded with metal ions, and placing the catalyst in a muffle furnace for calcining and activating the catalyst at the high temperature of 450-650 ℃, wherein the activation time is 2-6 h. According to the invention, the novel catalyst for catalyzing and synthesizing the picoline is prepared by loading metal ions in the SBA-15 mesoporous molecular sieve through a one-step method, the selectivity and the conversion rate of the picoline obtained by catalysis are high, the thermal stability of the catalyst is high, and the effective service life of the catalyst is long.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a novel picoline catalyst.
Background
The picoline is a key common compound of the three medicines and the intermediates of the three medicines, and is also an important raw material for daily chemical industry, feed, food additives and radial tire industry. Wherein, the 3-methylpyridine and the derivatives thereof are important chemical raw materials or organic intermediates and are widely applied to fine chemical industries such as pesticides, medicines and the like. The pesticides developed by the 3-methylpyridine and the derivatives thereof have super-efficient pesticides and herbicides, and high-efficient bactericides, and gradually form a large specific pesticide series. Particularly, the pyridylmethylamine compounds represented by imidacloprid, which are developed in recent years and have the same action mechanism with nicotine, are worthy of being mentioned, and the compounds become hot spots for research and development of pesticide circles at home and abroad due to the characteristics of systemic absorption, broad spectrum, high efficiency and the like.
Patent CN201410764200.4 discloses a catalyst for preparing pyridine from 3-methylpyridine and a preparation method thereof, wherein the catalyst for synthesizing pyridine and 3-methylpyridine is prepared by a ZSM11 molecular sieve, a rare earth Y molecular sieve and the like; patent CN200310117024.7 discloses a preparation method of a supported catalyst for synthesizing picoline, which adopts a method that phosphate and composite phosphate are supported on a silica sphere carrier, and a method of supporting metal ions by an impregnation method is used for preparing the catalyst for synthesizing picoline. The catalyst of which the carrier is ZSM11 and silica spheres has short catalyst reuse rate and short catalyst life, and the conversion rate and the yield of the catalytically synthesized 3-methylpyridine are low.
Disclosure of Invention
The invention aims to provide a preparation method of a novel picoline catalyst, which is characterized in that metal ions are loaded in an SBA-15 mesoporous molecular sieve by a one-step method to prepare the novel catalyst for catalytically synthesizing picoline, the selectivity and the conversion rate of the picoline obtained by catalysis are high, the thermal stability of the catalyst is high, and the effective service life of the catalyst is long, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing a novel picoline catalyst comprises the following steps:
step 1: stirring water, concentrated hydrochloric acid and P123 at 25-50 deg.C for 0.5-4 hr;
step 2: slowly dripping TEOS into the obtained solution for 10-24h, adding silicate containing metal ions and a compound silicate solution, and stirring the solution for 24-48h to obtain a milky suspension;
and step 3: transferring the suspension into a self-pressure kettle, crystallizing at 60-120 deg.C for 24-48h, vacuum filtering, and oven drying at 40-70 deg.C;
and 4, step 4: obtaining the SBA-15 molecular sieve catalyst loaded with metal ions, and placing the catalyst in a muffle furnace for calcining and activating the catalyst at the high temperature of 450-650 ℃, wherein the activation time is 2-6 h.
Further, the dosage of the silicate and the composite silicate is 1-40% of the weight of the SBA-15 molecular sieve carrier.
Further, the reaction mass ratio of the P123 to the water to the concentrated hydrochloric acid to the TEOS is 2:50:25: 10.
Further, the silicate is compounded by more than two of manganese silicate, magnesium silicate, cobalt silicate, zinc silicate and aluminum silicate.
Further, the silicate is a compound of more than two kinds of silicate, and the formula and the proportion are as follows:
manganese silicate: compounding aluminum silicate, wherein the molar ratio of the aluminum silicate to the aluminum silicate is 1: 0.05-1;
magnesium silicate: compounding aluminum silicate, wherein the molar ratio of the aluminum silicate to the aluminum silicate is 1: 0.05-1;
cobalt silicate: compounding aluminum silicate, wherein the molar ratio of the aluminum silicate to the aluminum silicate is 1: 0.05-1;
zinc silicate: the aluminum silicate is compounded, and the molar ratio is 1: 0.05-1.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the novel catalyst for catalyzing and synthesizing the picoline is prepared by loading metal ions in the SBA-15 mesoporous molecular sieve through a one-step method, the selectivity and the conversion rate of the picoline obtained by catalysis are high, the thermal stability of the catalyst is high, and the effective service life of the catalyst is long.
Detailed Description
The following examples will explain the present invention in detail, however, the present invention is not limited thereto. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Stirring 4.0g of P123, 100g of water and 25g of concentrated hydrochloric acid at 40 ℃ for 3 h; slowly dripping 10.0g of TEOS into the obtained solution for 20h, adding an aluminum silicate and manganese silicate solution into the solution, and stirring the solution for 24h to obtain a milky suspension; transferring the suspension into a self-pressure kettle, crystallizing at 90 ℃ for 24 hours, filtering, and drying at 70 ℃; the SBA-15 molecular sieve catalyst loaded with metal ions is obtained and is placed in a muffle furnace for high-temperature calcination and activation at 450 ℃ for 4 hours. Wherein the molar ratio of the solution of aluminium silicate and manganese silicate is 1:1(mol), and the dosage is 15% of the total mass of the system.
Example 2
Stirring 5.5g of P123, 120g of water and 30g of concentrated hydrochloric acid at 40 ℃ for 2 hours; slowly dripping 11.0g of TEOS into the obtained solution for 24 hours, adding an aluminum silicate and zinc silicate solution into the solution, and stirring the solution for 24 hours to obtain a milky suspension; transferring the suspension into a self-pressure kettle, crystallizing at 90 ℃ for 24 hours, filtering, and drying at 70 ℃; the SBA-15 molecular sieve catalyst loaded with metal ions is obtained and is placed in a muffle furnace for high-temperature calcination and activation at 450 ℃ for 4 hours. Wherein the molar ratio of the solutions of aluminium silicate and zinc silicate is 1:1(mol), the amount used being 20% of the mass of the overall system.
Example 3
Stirring 5g of P123, 100g of water and 50g of concentrated hydrochloric acid at 25 ℃ for 4 h; slowly dripping 10.0g of TEOS into the obtained solution for 18h, adding a magnesium silicate and aluminum silicate salt solution into the solution, and stirring the solution for 48h to obtain a milky suspension; transferring the suspension into a self-pressure kettle, crystallizing at 60 ℃ for 36h, filtering, and drying at 40 ℃; the SBA-15 molecular sieve catalyst loaded with metal ions is obtained and is placed in a muffle furnace for calcining and activating the catalyst at the high temperature of 550 ℃, and the activation time is 2 hours. Wherein the molar ratio of the solutions of aluminium silicate and zinc silicate is 1:1(mol), the amount used is 30% of the total system mass.
Example 4
Stirring 6g of P123, 125g of water and 60g of concentrated hydrochloric acid at 50 ℃ for 2 h; slowly dripping 12.0g of TEOS into the obtained solution for 10h, adding cobalt silicate and aluminum silicate salt solution into the solution, and stirring the solution for 24h to obtain milky suspension; transferring the suspension into a self-pressure kettle, crystallizing at 120 ℃ for 48h, filtering, and drying at 70 ℃; the SBA-15 molecular sieve catalyst containing metal ions is obtained and is placed in a muffle furnace for high-temperature calcination and activation at 650 ℃ for 6 hours. Wherein the molar ratio of the solutions of aluminium silicate and zinc silicate is 1:1(mol), the amount used being 40% of the mass of the overall system.
According to the invention, silicate and composite silicate are loaded on SBA-15 molecular sieve carrier sol by a one-step method, and aldehyde-ammonia reaction is catalyzed to generate 3-methylpyridine and pyridine, so that the conversion rate and yield of the 3-methylpyridine are greatly improved, and the stability and catalytic life of the catalyst are obviously improved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A method for preparing a novel picoline catalyst is characterized by comprising the following steps:
step 1: stirring water, concentrated hydrochloric acid and P123 at 25-50 deg.C for 0.5-4 hr;
step 2: slowly dripping TEOS into the obtained solution for 10-24h, adding silicate containing metal ions and a compound silicate solution, and stirring the solution for 24-48h to obtain a milky suspension;
and step 3: transferring the suspension into a self-pressure kettle, crystallizing at 60-120 deg.C for 24-48h, vacuum filtering, and oven drying at 40-70 deg.C;
and 4, step 4: obtaining the SBA-15 molecular sieve catalyst loaded with metal ions, and placing the catalyst in a muffle furnace for calcining and activating the catalyst at the high temperature of 450-650 ℃, wherein the activation time is 2-6 h.
2. The method for preparing a novel picoline catalyst according to claim 1 wherein the silicate and the complex silicate are used in an amount of 1% to 40% by weight based on the weight of the SBA-15 molecular sieve support.
3. The method for preparing a novel picoline catalyst according to claim 1 wherein the reaction mass ratio of P123, water, concentrated hydrochloric acid and TEOS is 2:50:25: 10.
4. The method for preparing a novel picoline catalyst according to claim 1 wherein the silicate is compounded with two or more of manganese silicate, magnesium silicate, cobalt silicate, zinc silicate and aluminum silicate.
5. The method for preparing a novel picoline catalyst according to claim 4 wherein the silicate is a composite of two or more silicates, the formulation and ratio of which are:
manganese silicate: compounding aluminum silicate, wherein the molar ratio of the aluminum silicate to the aluminum silicate is 1: 0.05-1;
magnesium silicate: compounding aluminum silicate, wherein the molar ratio of the aluminum silicate to the aluminum silicate is 1: 0.05-1;
cobalt silicate: compounding aluminum silicate, wherein the molar ratio of the aluminum silicate to the aluminum silicate is 1: 0.05-1;
zinc silicate: the aluminum silicate is compounded, and the molar ratio is 1: 0.05-1.
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| CN202010662908.4A CN111760584A (en) | 2020-07-10 | 2020-07-10 | Preparation method of novel picoline catalyst |
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| CN103406138A (en) * | 2013-02-06 | 2013-11-27 | 华南师范大学 | Preparation method of high-stability transition metal-modified SBA-15 catalyst for ozonation |
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